KR101599778B1 - Laminated polyester film and antireflection film - Google Patents

Abstract

The present invention provides a laminated polyester film which can suppress interference fringes when used as a base film of an antireflection film and is excellent in adhesiveness to a hard coat layer made of an active ray hardening type resin, .
The laminated polyester film of the present invention has a layer (S layer) comprising a polyester and a layer (C layer) containing a polyester resin (A) having a fluorene skeleton, The anti-wet heat bonding index measured by the method described in any of the above items (1) to (5) is not less than 3 and not more than 5.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a laminated polyester film and an antireflection film,

The present invention relates to a laminated polyester film which is excellent in adhesion to a hard coat agent comprising an active ray-curable resin and suppressing interference fringes when used as a base material of an antireflection film, and a laminated polyester film comprising an active ray- And an antireflection film laminated with a hard coat layer.

A laminated film provided with a hard coat layer on the surface of a film is widely used as an antireflection film, a film for a touch panel, and a nameplate film.

The recent expansion of the market for flat panel displays (FPD) represented by liquid crystal displays (LCDs), plasma displays (PDPs) and organic electroluminescence displays (organic EL) is remarkable, It has been strongly demanded to highly assign a function corresponding to a demand to a member to be applied to the apparatus.

Among them, the antireflection film for preventing the surface reflection of the display is formed by providing a hard coat layer on the triacetate film or polyester film as a base material for preventing scratching, providing a high refractive index layer and a low refractive index layer thereon, And the reflection prevention function is provided.

However, in recent years, an antireflection film in which a hard coat layer of a high refractive index is directly applied on a polyester film and a low-reflectance layer is provided on the hard coat layer is examined from the demand of low reflection, thinning, and cost reduction of the antireflection film have. In the antireflection film having such a constitution, interference fringes are liable to be generated due to poor adhesion and a difference in refractive index between the film and the hard coat layer or irregularity in thickness, resulting in poor visibility. When the adhesive layer is provided on the polyester film in order to improve the adhesiveness, the adhesive property is improved. However, since the refractive index difference between the adhesive layer and the high refractive index hard coat layer, which is generally lower than that of the polyester film, It is difficult to eliminate the interference pattern.

As a method of suppressing the interference fringes generated when a hard coat layer of a high refractive index is provided on such a polyester film, a method of copolymerizing a monomer containing an aromatic substituent such as a fluorene group with a resin used in the adhesive layer, (Patent Document 1). However, in a method in which a polyester film before completion of crystal orientation is subjected to a corona discharge treatment as required, and the crystal orientation is completed by coating, drying, stretching and heat treatment of this adhesive coating agent, A high refractive index resin often has a rigid chemical structure, and therefore, a large amount of a sulfonic acid base having high hydrophilicity must be used for water dispersion of the resin, so that there is a problem in adhesiveness under a high temperature and high humidity environment. Further, the resin obtained by copolymerizing a fluorene group generally tends to have a high glass transition temperature, resulting in insufficient followability in stretching, deteriorating the coating property in the in-line coating method, or causing fine cracks in the adhesive layer and deteriorating the film haze There was a problem.

In addition, studies have been made to increase the refractive index of this adhesive layer by providing this adhesive layer containing metal oxide fine particles having a high refractive index, such as titanium oxide particles, on the polyester film (Patent Document 2) And problems such as deterioration of the film haze due to occurrence of aggregated particles or particles and voids at the binder interface are likely to occur.

Further, studies have been made to increase the refractive index of this adhesive layer by providing this adhesive layer containing a water-soluble titanium chelate compound or a zirconium compound on a polyester film (Patent Document 3), but the content of titanium or zirconium in these chelate compounds is It is necessary to add a large amount of a chelate compound in order to improve the refractive index, and since the metal chelate compound is decomposed in the heat treatment, the decomposition product may degrade the quality of the anti-reflection film .

Japanese Unexamined Patent Application Publication No. 10-110091 Japanese Patent Application Laid-Open No. 2004-54161 Japanese Patent Application Laid-Open No. 2005-97571

An object of the present invention is to provide an optical adhesive film excellent in adhesion to a hard coat layer and suppression of interference fringes when used as a base material of an antireflection film, An object of the present invention is to provide an antireflection film in which a coating property in a coating method is realized at a high level, a laminated polyester film having excellent properties such as high refractive index, high strength and high heat resistance, and a hard coat layer laminated on one side thereof.
(1) A layer (C layer) containing a polyester resin (A) having a fluorene skeleton is directly laminated on a layer (S layer) made of polyester and the layer C (Aa-3) having a sulfonic acid group or a dicarboxylic acid component (Aa-3) having a sulfonic acid group and having an anti-wet heat adhesive index of not less than 3 and not more than 5, , And has a ternary or higher polyvalent carboxylic acid component (Aa-4) in the polyester resin (A), wherein the content of the polyester resin (A) is less than 0.1 mol% based on the amount of the carboxylic acid component (Aa).
(Method of obtaining anti-wet heat adhesion index)
1. An actinic ray curable resin (Pelnox Limited, product: XJC-0357-1: refractive index 1.67) constituting the hard coat layer was coated uniformly on the laminated polyester film using a bar coater so that the film thickness after curing became 1.5 탆 do.
2. Next, the total irradiation intensity was set to 300 mJ / cm 2 by a condensing type high-pressure mercury lamp (EYE GRAPHICS CO., LTD. Product H03-L31) having an irradiation intensity of 120 W / cm set at a height of 9 cm from the surface of the C layer Ultraviolet rays are irradiated and cured to obtain an optical laminated film in which a hard coat layer is laminated on the laminated film.
3. The resulting laminated optical film for optical is left in a constant-temperature and constant humidity chamber at a temperature of 70 ° C and a relative humidity of 90% for 250 hours to obtain a sample for anti-wet heat adhesion test.
4. Next, 100 cross-cuts of 1 mm 2 are put in the hard coat layer of the sample for anti-wet heat adhesion test. The work is performed in the order of 7 of JIS K5600-5-6 (1999) except for the following points.
ㆍ Test conditions and number of test: Regardless of the requirement in 7.1.1 of JIS K5600-5-6 (1999), test conditions shall be 23 ℃ and relative humidity of 65%. In addition, the number of tests shall be one.
Curing of test plates: Regardless of the requirement in 7.1.2 of JIS K5600-5-6 (1999), curing conditions shall be 23 ℃, relative humidity of 65% and curing time shall be 1 hour.
ㆍ Number of cuts: The number of cuts shall be 11, regardless of the requirement in 7.1.3 of JIS K5600-5-6 (1999).
ㆍ Cut interval: Regardless of the requirement in 7.1.4 of JIS K5600-5-6 (1999), the cut interval is 1mm.
ㆍ Cutting and removal of coating film by manual order: The provisions of 7.2.5 of JIS K5600-5-6 (1999) shall not be applied mutatis mutandis. That is, brushing using a brush is not performed. In addition, in Section 7.2.6 of JIS K5600-5-6 (1999), the provisions of the second paragraph ("the center of the tape is placed in a lattice in a direction parallel to one set of corner cuts as shown in Fig. 3, And the tape shall be flattened with fingers in a length exceeding 20 mm minimum ") and shall not be applied mutatis mutandis to other regulations. Cellotape tape (Cellotape (registered trademark) CT405AP manufactured by NICHIBAN CO., LTD.) Is used as the tape.
ㆍ The tape is attached by using a hand roller (Audio-technica corporation product HP515) and reciprocating three times at a roller moving speed of 5 cm / sec under a load of 19.6 N / m and applying pressure.
5. Then, the tape was peeled off at a rate of 10 cm / sec at a rate of 90 cm with respect to the surface direction of the hard coat layer to perform an adhesion test, and evaluation was carried out in five steps based on the number of remaining grids provided in the hard coat layer, It should be an index.
5: 100/100 (remaining number / number of measurement)
4: 90/100 or more, less than 100/100
3: 80/100 or higher, 90/100 or lower
2: 50/100 or more, less than 80/100
1: less than 50/100.
(2) The laminated polyester film according to (1), wherein the polyvalent carboxylic acid component (Aa-4) is a tetracarboxylic acid.

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(3) In the above (1) or (2), the C layer contains a cross-linking agent (B), and the content (a) of the polyester resin (A) (a) / (b) of (b) is 70/30 or more and 95/5 or less.

(4) In any one of (1) to (3), the cross-linking agent (B) is at least one cross-linking agent selected from the group consisting of a melamine cross-linking agent, an oxazoline cross-linking agent and a carbodiimide cross- .

(5) The laminated polyester film according to any one of (1) to (4), wherein the laminated polyester film has a spectral reflectance of 6.0 to 8.3% at a wavelength of 550 nm.

(6) The laminated polyester film according to any one of (1) to (5), wherein the layer thickness of the C layer is 2 to 20 nm.

(7) A laminated polyester film according to any one of the above (1) to (6), wherein a reflection layer formed by laminating a high refractive index hard coat layer and a low refractive index layer formed by using an active ray- Prevention film.

(8) The antireflection film according to (7), wherein the refractive index of the high refractive index hard coat layer is 1.63 to 1.75 and the refractive index of the low refractive index layer is 1.35 to 1.40.

EFFECTS OF THE INVENTION [

The laminated polyester film of the present invention suppresses interference fringes when a hard coat layer formed by using an active energy ray-curable resin on the surface of the C layer is suppressed, and at the same time, the initial adhesion with the hard coat layer, Excellent adhesion. The antireflection film obtained by laminating the high refractive index hard coat layer and the low refractive index layer on the laminated film of the present invention is excellent in antireflection property for suppressing interference fringes and reflection of external light, and moisture resistance adhesion under a high temperature and high humidity environment.

The laminated polyester film of the present invention needs to have a layer (S layer) comprising a polyester to be a substrate layer and a layer (C layer) containing a polyester resin (A) having a fluorene skeleton.

The polyester constituting the layer (S layer) comprising the polyester serving as the base layer is a general term for polymers having an ester bond as a main bonding chain of the main chain, and preferable polyesters include ethylene terephthalate, ethylene-2,6 And at least one kind of constituent component selected from naphthalate, butylene terephthalate, ethylene-?,? - bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate, Can be used. These constituents may be used alone or in combination of two or more kinds. Particularly, it is particularly preferable to use a polyester having ethylene terephthalate as a main constituent in consideration of quality, economical efficiency and the like. Further, in applications where heat acts on the base material, polyethylene-2,6-naphthalate which is excellent in heat resistance and rigidity is more preferable.

In addition, these dicarboxylic acid components and diol components may be partially copolymerized, and preferably 20 mol% or less.

The intrinsic viscosity (measured in o-chlorophenol at 25 占 폚 according to JIS K7367 (2000)) of the polyester described above is preferably 0.4 to 1.2 dl / g, more preferably 0.5 to 0.8 dl / g .

The polyester may contain various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, Or may be added to such an extent as not to deteriorate the characteristics. Particularly, the addition of fine particles often deteriorates the transparency characteristics such as light transmittance and haze, and when added, the particle size is as small as possible, and preferably about 1/4 or less of the visible light wavelength It is preferable to have a particle size, and the amount thereof is preferably small.

Further, in the present invention, it is preferable to use a biaxially oriented polyester film as the S layer using the polyester. Here, the term " biaxial orientation " refers to a biaxial orientation pattern by wide angle X-ray diffraction. The biaxially oriented polyester film can be generally obtained by stretching a polyester sheet in an unstretched state by 2.5 to 5 times in the sheet longitudinal direction and the transverse direction, respectively, and then performing heat treatment to complete the crystal orientation.

In addition, the S layer used in the present invention may be a laminated structure having two or more layers. As the laminated structure, for example, a composite film having an inner layer portion and a surface layer portion can be exemplified as a composite film in which substantially no particles are contained in the inner layer portion and a layer containing particles is provided in the surface layer portion. The polymer may be a homopolymer or a homopolymer. In the display application for the main purpose of the present invention, the S layer preferably contains no particles or the like because of its optical properties such as transparency.

The layer thickness of the S layer to be the base material is not particularly limited and may be suitably selected in accordance with the application, but is usually 10 to 500 탆, preferably 20 to 300 탆.

The laminated polyester film of the present invention needs to have a layer (C layer) containing a polyester resin (A) having a fluorene skeleton in addition to the above S layer.

The polyester resin (A) having a fluorene skeleton used in the present invention refers to a polyester resin having an ester bond in the main chain or side chain and can be obtained by the following method I) or II). Also, a method of using the dicarboxylic acid component (Aa), the glycol component (Ab) and the component (Ac) as a constituent and a method of polycondensation of them) may also be used in combination.

I) A method wherein the dicarboxylic acid component (Aa) and the glycol component (Ab) are used as components and subjected to a polycondensation reaction.

II) A method of polycondensation reaction using as a constituent component (Ac) having at least one alcoholic functional group (hydroxyl group) and at least one carboxyl group.

In the method I), the dicarboxylic acid component (Aa) is a mixture of a dicarboxylic acid component (Aa-1) having a fluorene skeleton and a dicarboxylic acid component (Aa-2) having no fluorene skeleton Respectively. Further, the glycol component (Ab) is distinguished by a glycol component (Ab-1) having a fluorene skeleton and a glycol component (Ab-2) having no fluorene skeleton. In the present invention, in order to introduce a fluorene skeleton into the polyester resin (A), a dicarboxylic acid component (Aa-1) having a fluorene skeleton and / or a glycol component (Ab-1) having a fluorene skeleton are copolymerized Is required.

In the method of II), the component (Ac) is distinguished by a component (Ac-1) having a fluorene skeleton and a component (Ac-2) having no fluorene skeleton. In the present invention, in order to introduce a fluorene skeleton into the polyester resin (A), it is necessary that the component (Ac-1) having a fluorene skeleton is copolymerized.

Hereinafter, details of the case of using the method I) as the polyester resin (A) having a fluorene skeleton (hereinafter also referred to as " fluorene copolymerized polyester resin (A) " , II) is the same as the method I).

First, in the present invention, the dicarboxylic acid component (Aa) includes an ester-forming derivative obtained by alkyl esterifying a dicarboxylic acid. The dicarboxylic acid component (Aa) includes not only the tricarboxylic acid but also the tricarboxylic acid having three or more valences. The dicarboxylic acid component (Aa) also includes an acid anhydride.

In the present invention, glycol component (Aa) includes not only narrow glycol but also trihydric or higher polyol.

Examples of the dicarboxylic acid component (Aa-1) having a fluorene skeleton include 9,9-bis (t-butoxycarbonylmethyl) fluorene, 9,9-bis [2- (t- Ethyl] fluorene, 9,9-bis [2- (t-butoxycarbonyl) -1-cyclohexylethyl ] Fluorene, 9,9-bis [2- (t-butoxycarbonyl) -1-phenylethyl] fluorene, 9,9- 9,9-bis [2- (t-butoxycarbonyl) -1-methylethyl] fluorene, 9,9- Bis [2- (t-butoxycarbonyl) butyl] fluorene, 9,9-bis [2- (t-butoxycarbonyl) (t-butoxycarbonyl) -1-methylbutyl] fluorene, 9,9-bis [5- (t-butoxycarbonyl) pentyl] fluorene, and the like.

As the dicarboxylic acid component (Aa-2) having no fluorene skeleton, an aromatic, aliphatic or alicyclic dicarboxylic acid having no fluorene skeleton or a trivalent or higher polyvalent carboxylic acid can be used. As the dicarboxylic acid component (Aa-2), terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2 , 6-naphthalene dicarboxylic acid, 1,2-bisphenoxyethane-p, p'-dicarboxylic acid, phenylindoxicarboxylic acid and the like. Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, dimeric acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

Examples of the glycol component (Ab-1) having a fluorene skeleton include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) Methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dimethylphenyl] ) -3-ethylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) 3-propylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3,5-dipropylphenyl] fluorene, (2-hydroxyethoxy) -3-isopropylphenyl] fluorene, 9,9-bis [4- Bis [4- (2-hydroxyethoxy) -3,5-di-n-butylphenyl] ] Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] 5-diisobutylphenyl] (2-hydroxyethoxy) -3- (1-methylpropyl) phenyl] fluorene, 9,9-bis [4- Bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- -Hydroxyethoxy) -3,5-diphenylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3- benzylphenyl] fluorene, 9,9- - (2-hydroxyethoxy) -3,5-dibenzylphenyl] fluorene, 9,9-bis [4- (3- hydroxypropoxy) phenyl] fluorene 9,9- 4-hydroxybutoxy) phenyl] fluorene, and the like, but are not limited thereto.

Examples of the glycol component (Ab-2) not having a fluorene skeleton include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4- 1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl- 5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2 , 4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylenediphenol, 4,4 '- (2-norbornylidene) di Phenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidene phenol, 4,4'-isopropylidene diol, cyclopentane- , 2-diol, cyclohexane 1,2-diol, cyclohexane-1,4-diol, and the like, but the present invention is not limited thereto.

The copolymerization amount of the dicarboxylic acid component (Aa-1) having a fluorene skeleton in the fluorene copolymerizable polyester resin (A) is preferably such that the dicarboxylic acid component (Aa) constituting the fluorene copolymerizable polyester resin (A) ) Is preferably at least 40 mol%, more preferably at least 80 mol%. The upper limit is not particularly limited, but is preferably 95 mol% or less.

The copolymerization amount of the glycol component (Ab-1) having a fluorene skeleton in the fluorene copolymerized polyester resin (A) is preferably from 1 to 10 parts by weight, based on the amount of the glycol component (Ab) constituting the fluorene copolymerized polyester resin Is preferably at least 40 mol%, more preferably at least 80 mol%. The upper limit is not particularly limited, but is particularly preferably 95 mol% or less.

When the copolymerization amount is less than 40 mol%, the refractive index of the fluorene copolymerized polyester resin (A) is insufficient, and there is a possibility that an interference fringe occurs when the hard coat layer is laminated. Although the upper limit is not particularly limited, when the copolymerization ratio is more than 95 mol%, the glass transition temperature of the fluorene copolymerized polyester resin (A) becomes high and the stretchability becomes poor, the handling property is deteriorated, When the C layer is formed by using the in-line coating method, there is a case in which a uniform C layer is not formed due to lack of followability of drawing.

The copolymerization amount of the dicarboxylic acid component (Aa-1) having a fluorene skeleton and the glycol component (Ab-1) having a fluorene skeleton in the fluorene copolymerized polyester resin (A) When the total amount of the dicarboxylic acid component (Aa) and the glycol component (Ab) constituting the ester resin (A) is 100 mol%, it is preferably 20 mol% or more, more preferably 40 mol% %. The upper limit is not particularly limited, but is preferably 50 mol% or less.

The laminated film of the present invention can be produced by applying an aqueous coating agent containing a fluorene copolymerized polyester resin (A) to the surface of the S layer, and drying and heat-treating the laminated film to laminate the C layer.

In order to obtain an aqueous coating agent containing the fluorene copolymerized polyester resin (A), the fluorene copolymerized polyester resin (A) is preferably water-soluble. To make the fluorene copolymerized polyester resin (A) water-soluble, it is preferable to introduce a hydrophilic component such as a compound containing a carboxylate group or a compound containing a sulfonate group into the side chain of the polyester resin (A). The introduction of such a hydrophilic component can be achieved by using a dicarboxylic acid component (Aa-3) having a sulfonic acid group as the dicarboxylic acid component (Aa) or a polyvalent carboxylic acid component (Aa-4) having a trivalent or more .

Examples of the dicarboxylic acid component (Aa-3) having a sulfonic acid group include sulfo isophthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene- Phenoxy] isophthalic acid, and alkaline earth metal salts.

As the trivalent or more polyvalent carboxylic acid component (Aa-4), an acid anhydride other than the polycarboxylic acid such as trimellitic acid may be used. Specific examples thereof include trimellitic anhydride, 1,2,4,5-butanetetracarboxylic acid dianhydride (anhydrous pyromellitic acid), 1,2,3,4-pentanetetracarboxylic acid dianhydride, 3,3 ' , 4,4'-benzophenonetetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 5 - (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, ethylene glycol bistrimellitate dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic acid dianhydride, thiophene -2,3,4,5-tetracarboxylic acid dianhydride, and ethylene tetracarboxylic acid dianhydride.

However, in applications where moisture resistance adhesion is required as represented by recent flat panel display applications, when a sulfonic acid base is used as the hydrophilic component of the polyester resin (A), the strength of the sulfonic acid base The adhesiveness under high temperature and high humidity conditions may be lowered.

Therefore, in the present invention, it is preferable that the fluorene copolymerized polyester resin (A) does not have a dicarboxylic acid component (Aa-3) having a sulfonic acid group or the dicarboxylic acid component Is preferably contained in an amount of less than 0.1 mol% based on the amount of the component (Aa). The amount of the dicarboxylic acid component (Aa-3) having a sulfonic acid group is more preferably 0.05% by mole or less, particularly preferably 0% by mole.

Therefore, in the present invention, when hydrophilicity (water-soluble) is imparted to the fluorene copolymer polyester resin (A), it is preferable to copolymerize the polyvalent carboxylic acid component (Aa-4) having three or more valences. A carboxyl group can be introduced into the side chain of the polyester resin (A) by copolymerizing a polyvalent carboxylic acid component (Aa-4) having three or more valences. The carboxyl group may be neutralized with ammonia, sodium hydroxide or the like to form a carboxylate group. By making carboxylate groups, hydrophilicity can be further increased.

Further, in the present invention, tetracarboxylic acid is more preferably used as the trivalent or more polyvalent carboxylic acid component (Aa-4). Since the tetracarboxylic acid has many carboxyl groups as compared with the trivalent carboxylic acid such as trimellitic acid, the tetracarboxylic acid has a large number of carboxyl groups in the dicarboxylic acid The proportion of the polycarboxylic acid component (Aa-4) in the carboxylic acid component (Aa) can be reduced. Thereby, the number average molecular weight when the polyester resin is polymerized can be sufficiently increased, and adhesion with an adherend such as a hard coat layer can be improved.

In the copolymerization of the polyvalent carboxylic acid component, a polyvalent carboxylic anhydride (Aa-4) having three or more valences is added to a polyester polyol (polyester oligomer) obtained by reacting a dicarboxylic acid component (Aa) and a glycol component (Ab) To introduce a carboxyl group into the side chain of the polyester resin (A). By using such a method, the carboxyl group can be more efficiently introduced into the side chain of the polyester resin (A).

The amount (Aa-4m (mol)) of the polycarboxylic acid anhydride (Aa-4) to be used is determined by the amount of the glycol component (Aa) used in the esterification reaction (Aam Is preferably 0.5 to 1.0 times the amount of the difference (Aam-Abm (mol)) of the amount of the component (Abm (mol)) of the component. If it is less than 0.5 times, the adhesion of the prepared polyester resin coating film to a substrate under high temperature and high humidity conditions may be lowered, and if it exceeds 1.0 times, the number average molecular weight of the polyester may not increase, which is not preferable.

When the fluorene copolymerized polyester resin (A) is water-soluble, a small amount of a water-soluble organic solvent may be contained from the viewpoints of storage stability and handling of the coating agent. Examples of the water-soluble organic solvent include water-soluble alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, water-soluble ketones such as acetone, water-soluble ethers such as methyl cellosolve, cellosolve, butyl cellosolve, carbitol and butyl carbitol do. These can be used singly or in combination. The content is preferably 10% or less, preferably 7% or less, more preferably 5% or less, with respect to the total amount of the coating agent in terms of explosion resistance and environmental pollution.

Next, an example of a method for producing the fluorene copolymerized polyester resin (A) will be described. First, succinic acid or an ester-forming derivative thereof as the dicarboxylic acid component (Aa-2) having no fluorene skeleton, and 9,9-bis [4- (2 -Hydroxyethoxy) phenyl] fluorene is subjected to an esterification reaction with a glycol component such as ethylene glycol and the like as a glycol component (Ab-2) having no fluorene skeleton to obtain a polyester polyol. At this time, the addition amount of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and ethylene glycol is preferably 1.01 to 2.0 moles per mole of the total dicarboxylic acid component. In order to polymerize the polyester polyol, an excessive glycol component is required for the dicarboxylic acid component, and thus a glycol component of 1.01-fold mol or more relative to the dicarboxylic acid component is required. However, when the molar ratio exceeds 2.0 mol, the number average molecular weight distribution of the polyester resin may not increase, which is not preferable.

Examples of the catalyst include a germanium-based catalyst such as a titanium-based or antimony trioxide antimony-based or germanium-based germanium such as tetraisopropyl titanate or tetra-n-butyl titanate; a catalyst such as zinc acetate, manganese acetate, dibutyltin oxide , And preferably tetra-n-butyl titanate is used. The amount of the catalyst to be added is preferably 10 to 1000 ppm based on the dicarboxylic acid component. If the amount is less than 10 ppm, the reaction may not proceed. On the other hand, if the amount exceeds 1000 ppm, there is no advantage such as shortening the reaction time. The esterification reaction at this time is not particularly limited in terms of temperature and time, but may be carried out within a known range. For example, it is usually carried out at 160 to 240 ° C for 1 to 10 hours while distilling water or an alcohol. Thereafter, the reaction system is gradually depressurized at about 200 to 260 DEG C and the reaction is performed at 0.01 to 0.5 MPa for about 0.1 to 3 hours.

Subsequently, the polycarboxylic acid anhydride (Aa-4) is added to the obtained polyester polyol. When the reaction is carried out at 160 to 200 ° C for about 1 to 10 hours, a desired polyester polyol is obtained. At this time, the catalyst may be added to the same extent.

In the present invention, the intrinsic viscosity of the fluorene copolymerized polyester resin (A) is not particularly limited, but is preferably 0.3 dl / g or more from the viewpoint of good adhesion with an object to be adhered such as a hard coat layer, More preferably 0.35 dl / g or more, and most preferably 0.4 dl / g or more. The upper limit of the intrinsic viscosity is not particularly limited, but is preferably 0.8 dl / g or less from the viewpoint of handling properties. The fluorene copolymerized polyester resin (A) having an intended intrinsic viscosity is obtained by controlling the melt polymerization conditions such as the polymerization time and the polymerization temperature.

The glass transition point (hereinafter, sometimes abbreviated as Tg) of the fluorene copolymerized polyester resin (A) is preferably 50 to 170 ° C, more preferably 50 to 150 ° C. If the Tg is less than 50 deg. C, the moisture-resistant adhesive property tends to deteriorate. On the other hand, if the Tg exceeds 150 deg. C, the C layer may not be uniformly applied in the in-line coating method described later. In order to keep the Tg within the above range, an aliphatic dicarboxylic acid component (Aa-2) other than the dicarboxylic acid component having a fluorene skeleton of the fluorene copolymerized polyester resin (A) .

The acid value of the fluorene copolymerized polyester resin (A) is preferably 20 mgKOH / g or more, and more preferably 30 mgKOH / g or more. By setting the acid value within the above range, the adhesiveness, particularly the moisture resistance adhesion, can be improved. To adjust the acid value to the above range, the amount of the polycarboxylic acid anhydride (Aa-4) to be reacted with the polyester polyol in the polymerization of the fluorene copolymerized polyester resin (A) is adjusted.

Further, in the present invention, the content of the fluorene copolymer polyester resin (A) in the C layer is preferably 70% by weight or more based on the entire C layer. The upper limit is not particularly limited, but 100% by weight is a practical upper limit.

By setting the content of the fluorene copolymerizable polyester resin (A) within the above range, the refractive index of the C layer can be improved and the difference in refractive index between the base layer, the C layer and the hard coat layer can be reduced, and the interference fringe can be reduced.

Further, it is preferable that the C layer contains a crosslinking agent (B) in addition to the fluorene copolymerized polyester resin (A) from the viewpoint of improvement in anti-wet heat adhesion.

When the crosslinking agent (B) is contained in the C layer, the total (a + b) of the content (a) of the fluorene copolymerizable polyester resin (A) and the content It is preferable to adjust it to 90 wt% or more. By setting the total content (a + b) within the above range, the refractive index of the C layer can be increased. The upper limit of the total content (a + b) is not particularly limited, but 100% by weight is a practical upper limit.

Further, in the present invention, by using at least one crosslinking agent selected from the group consisting of a melamine crosslinking agent, an oxazoline crosslinking agent and a carbodiimide crosslinking agent as the crosslinking agent (B), it is possible to prevent the carboxyl group of the fluorene copolymerized polyester resin Heat-resistant adhesiveness by the cross-linking agent (B), and improvement of adhesiveness against moisture and heat due to progress of the self-crosslinking reaction of the cross-linking agent (B). The content of the cross-linking agent (B) such as a melamine-based, oxazoline-based or carbodiimide-based cross-linking agent in the C layer is not particularly limited, and two or more cross-linking agents may be used.

The melamine-based crosslinking agent used in the present invention is not particularly limited, but may be a melamine, a methylolated melamine derivative obtained by condensing melamine and formaldehyde, a compound partially or completely etherified by reacting methylolated melamine with a lower alcohol, And the like can be used. As the melamine-based crosslinking agent, any of monomers and condensates composed of dimers of dimers or more may be used, or a mixture thereof may be used. As the lower alcohol used in the etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like can be used. Examples of the functional group include an imino group-containing methylol melamine resin, a methylol group-type melamine resin, a methylol group-type methylated melamine resin, a fully alkyl-type methylated melamine resin having an alkoxy methyl group such as imino group, methylol group or methoxymethyl group or butoxymethyl group in one molecule. Resin. Among them, a methylolated melamine resin is most preferable. An acidic catalyst such as p-toluenesulfonic acid may be used in order to accelerate the thermosetting of the melamine crosslinking agent.

The oxazoline crosslinking agent used in the present invention is not particularly limited as long as it has an oxazoline group as a functional group in the above-mentioned compound, but it may contain at least one monomer containing an oxazoline group, And an oxazoline group-containing copolymer obtained by copolymerizing monomers.

Examples of the monomer containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2- 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be used. have. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.

In the oxazoline-based crosslinking agent, at least one other monomer used for the monomer containing an oxazoline group is not particularly limited as long as it is a monomer copolymerizable with the oxazoline group-containing monomer, and examples thereof include methyl acrylate, methacryl Acrylic acid esters or methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, Unsaturated carboxylic acids such as methacrylic acid, itaconic acid and maleic acid, unsaturated nitriles such as acrylonitrile and methacrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide Unsaturated amides, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, , Olefins such as ethylene and propylene, halogen-containing?,? - unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride, and?,? - unsaturated aromatic monomers such as styrene and? These may be used alone or in a mixture of two or more.

The carbodiimide-based crosslinking agent used in the present invention is particularly limited as long as it has a carbodiimide group as a functional group or a compound having one or more cyanoamide groups in the molecule thereof in the molecule It is not. Specific examples of such carbodiimide compounds include dicyclohexylmethanecarbodiimide, dicyclohexylcarbodiimide, tetramethylxyidenecarbodiimide, and urea-modified carbodiimide, and they may be one or two Mixtures of two or more species may be used.

(A) / (b) of the content (a) of the fluorene copolymerized polyester resin (A) and the content (b) of the crosslinking agent (B) in the C layer is preferably 70/30 to 95/5 Do. When the weight ratio (a) / (b) is less than 70/30, the refractive index of the C layer is insufficient to cause an interference fringe when a hard coat layer of high refractive index is provided on the surface of the C layer. On the other hand, if the weight ratio (a) / (b) exceeds 95/5, the anti-wet heat adhesion with the hard coat layer is lowered and the practicality is lowered.

The C layer of the laminated polyester film of the present invention may contain various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, Dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, and the like.

Particularly, as a preferred form of the present invention, it is more preferable to contain fine particles in the C layer because the lubricity and anti-blocking property are improved.

The fine particles to be contained are not particularly limited, and examples thereof include inorganic particles such as colloidal silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, carbon black and zeolite particles, acrylic particles, silicone particles, polyimide particles, Teflon Crosslinked polyester particles, crosslinked polystyrene particles, crosslinked polymer particles and core shell particles, and any of these particles may be used, or a plurality of such particles may be used in combination.

The number average primary particle diameter of these particles is preferably in the range of 0.01 to 0.4 mu m. Here, the average primary particle diameter is an average of the particle diameters of primary particles defined as particles generated by the growth of a single crystal nucleus in JIS-H7008 (2002). The particle diameter of the primary particles (hereinafter referred to as primary particle diameter) is the average value of the long diameter and the short diameter. With respect to the measurement of the average primary particle size, the sample was observed at a magnification of 50,000 times using a scanning electron microscope (SEM) according to JIS-H7804 (2005), and the long diameter and the short diameter of each primary particle Average primary particle size can be obtained from the number average of the primary particles by measuring the primary particle diameter from the average and determining the same primary particle diameter for 100 primary particles. When the average primary particle diameter of the particles is less than 0.01 탆, the particles may agglomerate to deteriorate the haze of the C layer. On the other hand, when the average primary particle diameter exceeds 0.4 탆, There is a possibility that the particles fall off depending on the thickness of the C layer. The average primary particle size of the particles is more preferably in the range of 20 to 300 nm, and more preferably in the range of 20 to 200 nm. The particles may be monodisperse particles or aggregated particles in which a plurality of particles are aggregated. Further, in some cases, plural kinds of particles having different average primary diameters may be used in combination. The addition amount of the particles should be appropriately controlled and designed depending on the thickness of the C layer, the resin composition, the average primary particle size, the required lubricity and the intended use, but is preferably in the range of 0.05 to 8 parts by weight based on 100 parts by weight of the entire C layer And more preferably 0.1 to 5 parts by weight.

In the laminated polyester film of the present invention, it is necessary that the surface of the C layer has an anti-wet heat adhesive index of 3 or more and 5 or less. The laminated polyester film of the present invention can be made into an antireflection film by laminating a high refractive index hard coat layer and a low refractive index layer on the surface of the C layer. However, even if the laminate polyester film has an anti- It is possible to suppress deterioration of the adhesion of the hard coat layer and can be suitably used in applications requiring moisture resistance adhesion. The anti-wet heat adhesive index is preferably 3 or more and 5 is the upper limit. Details of the method of measuring the anti-wet heat adhesion index will be described later.

As a method of setting the anti-wet heat adhesion index within the above range, it is preferable that the fluorene copolymerized polyester resin (A) has no dicarboxylic acid component (Aa-3) having a sulfonic acid group or the fluorene copolymerized polyester resin Of the dicarboxylic acid component (Aa) is less than 0.1 mol% based on the amount of the dicarboxylic acid component (Aa). Further, by adding the above-mentioned crosslinking agent to the C layer, the anti-wet heat bonding index can be further improved.

The spectral reflectance of the laminated polyester film of the present invention at a wavelength of 550 nm is preferably in the range of 6.0 to 8.3% in suppressing interference fringes with the hard coat layer. , More preferably 6.5 to 8.3%, and most preferably 6.5 to 8.0%. If the spectral reflectance is out of the above range, a negative effect due to interference hardly occurs and interference patterns with the hard coat layer are generated, which is not preferable. (Aa-1) having a fluorene skeleton and the glycol component (Ab-1) having a fluorene skeleton in the fluorene copolymerized polyester resin (A) in order to keep the spectral reflectance within the above- Can be attained by adjusting the amount of water.

The layer thickness of the C layer is preferably in the range of 2 to 200 nm, more preferably in the range of 2 to 100 nm, still more preferably in the range of 2 to 20 nm in order to suppress interference fringes with the hard coat layer to be. If the thickness of the C layer is excessively large, it is difficult to cause a negative effect due to the interference due to the optical path difference, so that interference fringes are liable to be generated when the hard coat layer is provided, which is not preferable. On the other hand, if it is too thin, the adhesion to the hard coat layer may decrease, which is not preferable.

In the present invention, as a method of obtaining a laminated film having an S layer and a C layer, a method of laminating a C layer on the S layer and the like are listed. Among them, a method of coating (coating) a coating agent constituting the C layer on the S layer and laminating it is preferable. As such a coating method, a method of performing coating in a process different from the manufacturing process of the S layer, a so-called off-line coating method, and a so-called " laminated polyester film " There is an in-line coating method. However, in the present invention, it is preferable to employ an in-line coating method in terms of the cost and the uniformity of the coating thickness. In this case, the solvent of the coating liquid used is most preferably water-based in view of environmental pollution and explosion resistance .

As a method of applying the water-based coating agent in the practice of the present invention, for example, a reverse coat method, a spray coat method, a bar coat method, a gravure coat method, a rod coat method and a die coat method can be used. It is not.

In the present invention, the surface of the S layer, which is the substrate layer, is subjected to corona discharge treatment or the like before application of the aqueous coating agent, and the wet tension of the surface is preferably 47 mN / m or more, more preferably 50 mN / m or more . The adhesiveness between the C layer and the S layer is improved and the coatability is improved.

Next, the case of using the polyethylene terephthalate (hereinafter abbreviated as PET) film as the S layer is described as an example of the method for producing the laminated polyester film of the present invention, but the present invention is not limited thereto.

The PET pellets having an intrinsic viscosity of 0.5 to 0.8 dl / g constituting the S layer were vacuum dried and then fed to an extruder, melted at 260 to 300 ° C, extruded from the T-shaped pellet into a sheet, Wound on a mirror casting drum at 10 to 60 DEG C, cooled and solidified to produce an unoriented PET film. This unstretched film is stretched 2.5 to 5 times in the longitudinal direction (referred to as " longitudinal direction ") between rolls heated at 70 to 100 캜. At least one surface of the film was subjected to corona discharge treatment in the air to prepare a fluorene copolymerized polyester resin (A) having a wet tensile strength of 47 mN / m or more on the surface thereof and constituting a C layer on the treated surface (dicarboxylic acid (Aa-3) having a sulfonic acid group as a component (Aa)) and an aqueous coating agent comprising a cross-linking agent (B) as a main component are applied. The applied laminated film is gripped with a clip and introduced into a drying zone. After drying at a temperature lower than the Tg of the polyester resin constituting the S layer, the laminated film is raised to a temperature of Tg or higher and dried again at a temperature near Tg, In a heating zone at 70 to 150 DEG C in a transverse direction (also referred to as " transverse direction "), and subsequently stretched by 2.5 to 5 times in a heating zone at 200 to 240 DEG C For 40 seconds to obtain a polyester film in which the C layer is laminated on the S layer on which the crystal orientation is completed. During the heat treatment, a relaxation treatment of 3 to 12% may be carried out if necessary. The biaxial stretching may be any one of longitudinal, transverse sequential stretching, and simultaneous biaxial stretching, and may be repeated in any one of the longitudinal, transverse stretching, longitudinal and transverse stretching directions. The thickness of the laminated polyester film is not particularly limited, but is preferably 3 to 300 mu m. The coating agent used in this case is preferably an aqueous coating agent in view of environmental pollution and explosion resistance.

The surface of the C layer of the thus-obtained laminated polyester film according to one embodiment of the present invention is excellent in adhesiveness to a hard coat layer formed by using an actinic ray curable resin, and the C layer is a fluorene Since the copolymer polyester resin (A) is contained, the refractive index difference when the high refractive index hard coat layer is provided on the surface of the C layer can be made small, and the suppression of the interference fringe can be made excellent. Further, when the dicarboxylic acid component (Aa-3) having a sulfonic acid group as a hydrophilic component is not contained, deterioration of adhesion with the hard coat layer under high temperature and high humidity conditions can be suppressed to the extreme. In addition, the addition of the crosslinking agent (B) improves the coating property and makes it possible to obtain not only a coating film (C layer) with less coating unevenness but also a stronger adhesion with the hard coat layer. Such a laminated polyester film can be used for a display member such as a hard coat film, an antireflection film provided with a low refractive index layer thereon, a laminated film for a touch panel provided with a conductive metal oxide layer, a laminated film for an electronic paper, And can be used as a film.

Next, the optical laminated film provided with the hard coat layer on the laminated polyester film of the present invention will be described.

In the present invention, the material constituting the hard coat layer is not particularly limited and may be any material that transmits visible light, but it is preferable that the light transmittance is high. Examples of the material to be used include acrylic resin, polycarbonate resin, vinyl chloride resin, polyester resin, urethane resin, and active ray curable resin. Particularly, acrylic resin, urethane resin, and active ray-curable resin can be suitably used in terms of scratch resistance, productivity, and the like.

The active ray curable resin used as the constituent component of the hard coat layer according to the present invention is preferably at least one member selected from the group consisting of pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, trimethylol propane tri (Meth) acrylate, 2,2-bis (4- ((meth) acryloyloxyphenyl) (Meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, Propane, 2,2-bis (4- (meth) acryloylpenta (Meth) acryloyloxypropane) propane, 2,2-bis (4- (meth) acryloyloxyindane Dibromophenyl) propane, 2,2-bis (4 (meth) acryloyloxypentaethoxy-3,5-dibromophenyl) (Meth) acryloyloxyethoxy-3,5-dimethylphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxy- (Meth) acryloyloxyphenyl) sulfone, bis (4- (meth) acryloyloxyethoxyphenyl) sulfone, bis (Meth) acryloyloxyethoxy-3-phenylphenyl) sulfone, bis (4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl) sulfone, bis (Meth) acryloyloxypentoxyphenyl) sulfide, bis (4- (meth) acryloyloxyethoxyphenyl) sulfide, bis (Meth) acryloyloxyethoxy-3, 5-dimethylphenyl) sulfide, di ((meth) acryloyloxyethoxy) phosphate (Meth) acryloyloxyethoxy) phosphate, and tri (meth) acryloyloxyethoxy) phosphate. These polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more.

In order to control the hardness, transparency, strength, refractive index and the like of the active ray curable resin together with these polyfunctional (meth) acrylic compounds, it is possible to use styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, (Meth) acrylate, benzyl (meth) acrylate, biphenyl (meth) acrylate, diallyl phthalate, dimethalyl phthalate, , Diallylbiphenylate, or a reaction product of (meth) acrylic acid with a metal such as barium, lead, antimony, titanium, tin or zinc. One or more of these may be used.

In the present invention, the term " (meth) acrylic compound " is abbreviated as " methacrylic compound and acrylic compound "

As a method for curing the active ray curable resin in the present invention, for example, a method of irradiating ultraviolet rays can be used, but in this case, it is preferable to add about 0.01 to 10 parts by weight of a photopolymerization initiator to the compound .

The active ray curable resin used in the present invention may contain an organic solvent such as isopropyl alcohol, ethyl acetate, methyl ethyl ketone or the like in the range of not damaging the effect of the present invention for the purpose of improving the workability at the time of coating and controlling the thickness of the coating film Can be blended.

In the present invention, the active line means an electromagnetic wave for polymerizing an acrylic vinyl group such as ultraviolet ray, electron beam, radiation (alpha rays, beta rays, gamma rays) and is practically preferable because of ultraviolet rays. Examples of the ultraviolet source include ultraviolet fluorescent lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, carbon arc lamps and the like. In addition, the electron beam system is advantageous in that the apparatus is expensive and requires operation under an inert gas, but it is not necessary to include a photopolymerization initiator, a photosensitizer or the like.

The hard coat layer according to the present invention can be formed into a high refractive index hard coat layer by containing, for example, metal oxide fine particles. Examples of such metal oxide fine particles include titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, indium tin oxide (ITO), antimony doped tin oxide Zinc dope oxide, zinc dope oxide, zinc dope oxide, zinc dope oxide, zinc dope oxide, zinc dope oxide, zinc dope oxide, and zinc oxide.

The content of the metal oxide fine particles in the high refractive index hard coat layer is preferably 20 to 90 parts by weight, more preferably 30 to 80 parts by weight, based on 100 parts by weight of the resin component composed of the (meth) acrylic compound Do.

In the present invention, the thickness of the hard coat layer should be appropriately controlled depending on the refractive index of the C layer or the hard coat layer, the intended use, and the like, and is not particularly limited, but is usually 1 to 10 탆, preferably 2 to 5 Mu m. When the thickness of the hard coat layer is within this preferable range, the hard coat property is sufficiently exhibited, and the film is not curled by the shrinkage at the time of curing of the hard coat layer.

In the present invention, it is preferable to provide an antireflection layer for suppressing glare on the surface of the hard coat layer, or to perform an antifouling treatment for preventing contamination.

Particularly, in the present invention, it is particularly preferable that a low refractive index layer which is an antireflection layer is laminated on the surface of the high refractive index hard coat layer of the laminated film for optical and used as an antireflection film.

The antireflection layer is not particularly limited, but it can be formed by stacking a low refractive index compound or by sputtering or vapor deposition of an inorganic compound such as magnesium fluoride or silicon oxide. The antifouling treatment can be carried out with an antifouling treatment with a silicone resin, a fluorine resin or the like.

In the present invention, it is particularly preferable to improve the antireflection performance by setting the refractive index of the high refractive index hard coat layer to 1.63 to 1.75 and the refractive index of the low refractive index layer to 1.40 or less.

The refractive index of the low refractive index layer laminated on the high refractive index hard coat layer is preferably 1.40 or less as described above, but the lower limit of the refractive index of the low refractive index layer is 1.30. And the refractive index of the low refractive index layer is more preferably 1.35 to 1.40. In order to improve the antireflection performance, the thickness of the low refractive index layer is preferably in the range of 70 to 160 nm, more preferably 80 to 140 nm, and still more preferably 85 to 105 nm.

Hereinafter, a method of measuring the refractive index of the high refractive index hard coat layer and the low refractive index layer will be described.

First, a coating agent for forming a high refractive index hard coat layer or a low refractive index layer is applied on the test piece D for film measurement (manufactured by ATAGO CO., LTD.) So that the film thickness of the coating film is about 3 μm.

Subsequently, the coating film is irradiated with ultraviolet rays so as to have a cumulative irradiation intensity of 400 mJ / cm 2 using a condensing type high-pressure mercury lamp (manufactured by EYE GRAPHICS CO., LTD., H03-L31), and the coating film is cured. An industrial UV checker (UVR-N1 manufactured by JAPAN STORAGE BATTERY CO., LTD.) Is to be used for measuring the cumulative irradiation intensity of ultraviolet rays.

The refractive index of the coated film after curing in an environment of 23 캜 and a relative humidity of 65% was measured using Abbe's refractive index NAR-1T (manufactured by ATAGO CO., LTD.).

Subsequently, the low refractive index layer will be described more specifically.

The low refractive index layer is preferably formed by curing a composition comprising silica-based fine particles or a fluorine-containing compound and an active ray-curable resin. The silica-based fine particles and the fluorine-containing compound may be used alone or in combination.

As the silica-based fine particles, silica-based fine particles (hollow silica fine particles) having cavities therein are preferably used because they can lower the refractive index of the low refractive index layer.

Examples of the silica-based fine particles having a cavity therein include silica-based fine particles having a cavity surrounded by an outer shell, porous silica-based fine particles having a large number of cavities, and the like are preferably used. The silica-based fine particles having cavities therein can be produced, for example, by the method disclosed in Japanese Patent No. 3272111, and those generally available on the market can be used.

The content of the silica-based fine particles is preferably in the range of 20 to 90% by mass with respect to 100% by mass of the total components of the low refractive index layer.

Examples of the fluorine-containing compound include fluorine-containing monomers and fluorine-containing polymer compounds.

Examples of the fluorine-containing monomer include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) Containing (meth) acrylic acid esters such as acrylate.

As the fluorine-containing polymer compound, for example, a fluorine-containing copolymer containing a fluorine-containing monomer and a monomer for imparting a crosslinkable group as a constituent unit is listed. Specific examples of the fluorine-containing monomer unit include fluoroolefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2 (For example, VISCOAT 6FM (manufactured by OSAKA ORGANIG CHEMICAL INDUSTRY LTD.) Or M-2020 (manufactured by DAIKIN INDUSTRIES, LTD.)), A partially or completely fluorinated alkyl ester derivative of (meth) , Etc.), fully or partially fluorinated vinyl ethers, and the like. Examples of the monomer for imparting a crosslinkable group include a (meth) acrylate monomer having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group or the like in addition to a (meth) acrylate monomer having a crosslinkable functional group in advance in the molecule such as glycidyl methacrylate (Meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allylacrylate, and the like.

The content of the fluorine-containing compound is preferably in the range of 5 to 90% by weight based on 100% by weight of the total components of the low refractive index layer.

As the above active ray curable resin, those same as the active ray curable resin used as a component of the hard coat layer can be used.

The content of the active ray curable resin is preferably in the range of 20 to 90% by weight based on 100% by weight of the total components of the low refractive index layer.

The method of curing the active ray curable resin may be the same as the method of curing the active ray curable resin in the hard coat layer.

[Method of measuring characteristics and evaluation method of effect]

A method of measuring the characteristics and an evaluation method of the effects in the present invention are as follows.

(1) Layer thickness of C layer

The cross section of the laminated film was cut into ultra-thin sections and observed under the following conditions where the cross-sectional structure could be observed with a TEM (transmission electron microscope) by a stained ultra slicing method by RuO ₄ staining, OsO ₄ staining or double staining of both , And the thickness of the C layer was measured from the cross-sectional photograph.

ㆍ Measuring apparatus: transmission electron microscope (H-7100FA type, Hitachi, Ltd.)

ㆍ Measurement condition: Acceleration voltage 100kV

ㆍ Sample adjustment:

ㆍ Magnification: 300,000 times.

(2) Spectral reflectance

The spectral reflectance was measured by bubbling a 50 mm wide black glossy tape (vinyl tape No. 200-50-21: black, manufactured by YAMATO Co., Ltd.) on the back surface of the C layer (in the case of double-side application, (Hitachi, Ltd. product 130-0632) and a 10 ° inclined spacer were attached to a spectrophotometer (U3410 manufactured by Hitachi, Ltd.), and the incident angle was 10 ° The spectral reflectance was measured. In addition, we used a part of the Al ₂ O ₃ plate as standard reflection plate to screen based on the reflectance.

(3) Interference pattern

(Pelnox Limited, product XJC-0357-1: refractive index: 1.67) constituting the hard coat layer was uniformly coated on the laminated polyester film with a bar coater so that the film thickness after curing became 1.5 탆.

Subsequently, ultraviolet rays were irradiated at a total irradiation intensity of 300 mJ / cm 2 with a condensing type high pressure mercury lamp (EYE GRAPHICS CO., LTD. Product H03-L31) having an irradiation intensity of 120 W / cm set at a height of 9 cm from the surface of the C layer And cured to obtain an optical laminated film in which a hard coat layer was laminated on the laminated film. An industrial UV checker (UVR-N1 manufactured by JAPAN STORAGE BATTERY CO., LTD.) Was used to measure the intensity of UV irradiation. The refractive index of the hard coat layer was 1.67.

Subsequently, a sample having a size of 8 cm (in the laminated polyester film width direction) × 10 cm (length direction of the laminated polyester film) was cut out from the obtained optical laminated film, and a black glossy tape (YAMATO Co., Ltd.) was coated on the opposite surface of the hard coat layer. Product vinyl tape No. 200-50-21: black) were bonded so as not to contain bubbles.

The sample was placed in a dark room at 30 cm directly below a 3-wavelength fluorescent lamp (F-L 15EX-N 15W, manufactured by Matsushita Electric Industrial Co., Ltd.), and the degree of interference fringe And the following evaluation was made. B of practical level is said, and A or more is said to be good.

S: Interference pattern is hardly visible

A: A little interference pattern is seen.

B: We see weak interference pattern

C: Strong interference pattern

(4) Initial adhesion

A laminate film for optical use was obtained in the same manner as in (3).

Next, 100 cross cuts of 1 mm < 2 > were placed in the hard coat layer of the optical laminated film. The operation was carried out in accordance with the procedure of Clause 7 of JIS K5600-5-6 (1999) except for the following points.

ㆍ Test conditions and number of test: Regardless of the requirement in 7.1.1 of JIS K5600-5-6 (1999), the test conditions were 23 ℃ and 65% relative humidity. In addition, the number of tests was set to one.

Curing of test plates: Regardless of the requirement in 7.1.2 of JIS K5600-5-6 (1999), curing conditions were 23 ℃, relative humidity 65%, and curing time was 1 hour.

ㆍ Number of cuts: Regardless of rule 7.1.3 of JIS K5600-5-6 (1999), the number of cuts is 11.

ㆍ Cut interval: Regardless of the rule in 7.1.4 of JIS K5600-5-6 (1999), the cut interval is 1mm.

ㆍ Cutting and removal of coating film by manual order: The provisions of 7.2.5 of JIS K5600-5-6 (1999) shall not be applied mutatis mutandis. That is, brushing using a brush is not performed. In addition, in Section 7.2.6 of JIS K5600-5-6 (1999), the provisions of the second paragraph ("the center of the tape is placed in a lattice in a direction parallel to one set of corner cuts as shown in Fig. 3, And the tape shall be flattened with fingers in a length exceeding 20 mm minimum ") and shall not be applied mutatis mutandis to other regulations. Cellotape tape (Cellotape (registered trademark) CT405AP manufactured by NICHIBAN CO., LTD.) Is used as the tape.

The attachment of the tape was carried out by using a hand roller (HP515, Audio-technica corporation) and reciprocating three times at a roller moving speed of 5 cm / sec under a load of 19.6 N / m to apply pressure. Subsequently, the tape was peeled at a rate of 10 cm / sec at an initial speed of 90 degrees with respect to the surface direction of the hard coat layer, and the four-step evaluation was carried out based on the number of remaining grids provided in the hard coat layer. S and A were called good adhesion.

S: 100/100 (remaining number / number of measurements)

A: 90/100 or higher, 100/100 or lower

B: 80/100 or higher, 90/100 or lower

C: Less than 80/100.

(5) The wet heat adhesion index

A laminate film for optical use was obtained in the same manner as in (3). The obtained optical laminated film was allowed to stand in a constant-temperature and constant humidity chamber at a temperature of 70 캜 and a relative humidity of 90% for 250 hours to obtain a sample for anti-wet heat adhesion test. The adhesion test for the obtained anti-wet heat adhesion test was carried out in the same manner as in (4), and the evaluation was carried out in five steps based on the number of remaining lattices. 4 or more is said to be good in anti-wet heat adhesion, 3 is set to practical level, and 2 or less is said to be poor in anti-wet heat adhesion.

5: 100/100 (remaining number / number of measurement)

4: 90/100 or more, less than 100/100

3: 80/100 or higher, 90/100 or lower

2: 50/100 or more, less than 80/100

1: less than 50/100.

(6) Interference pattern of anti-reflection film

The evaluation of the interference fringes of the antireflection film was carried out by observing the degree of interference fringes by visual observation in the same manner as in (3). B of practical level is said, and A or more is said to be good.

S: Interference pattern is hardly visible

A: A little interference pattern is seen.

B: We see weak interference pattern

C: Strong interference pattern

(7) Initial adhesion of antireflection film

The antireflection film was subjected to an adhesion test in the same manner as in (4), and evaluated in four stages according to the number of remaining lattices to be referred to as an initial adhesion property of the antireflection film. S and A were called good adhesion.

S: 100/100 (remaining number / number of measurements)

A: 90/100 or higher, 100/100 or lower

B: 80/100 or higher, 90/100 or lower

C: Less than 80/100.

Example

EXAMPLES The present invention will be described based on the following examples and comparative examples, but the present invention is not limited thereto. In addition, the adjustment method of the resin and the like used in each of the examples and comparative examples is shown as a reference example.

(Reference Example 1) Preparation of Fluorene Copolymerized Polyester Resin (A-1)

Bis (4- (2-tert-butoxycarbonyl) aminophenol) as a glycol component (Ab-1) having 75 molar parts of dimethyl succinate as a dicarboxylic acid component (Aa-2) having no fluorene skeleton under a nitrogen gas atmosphere, (Ab-2) as a glycol component (Ab-2) having no fluorene skeleton were fed into an ester exchange reactor, and tetrabutyl titanate (catalyst) 100 parts by weight of a vinyl ester derivative (dimethyl succinate) was added in an amount of 100 parts by weight, followed by esterification reaction at 160 to 200 ° C for 5 hours, followed by distillation of methanol. Further, the reaction was carried out at 240 캜 under a reduced pressure of 0.2 MPa for 30 minutes to obtain a polyester polyol.

Subsequently, 25 parts by mol of 1,2,4,5-benzenetetracarboxylic acid dianhydride, which is a trivalent or higher polyvalent carboxylic acid component (Aa-4), is added to the polyester polyol, and the mixture is reacted at a reaction temperature of 160 to 180 DEG C for 3 hours And the reaction was carried out to obtain a fluorene copolymerized polyester resin (A-1). The Tg of the polyester resin was 99 ° C. The copolymerization amount of the glycol component (Ab-1) having a fluorene skeleton of the fluorene copolymerizable polyester resin (A-1) is preferably the sum of the amount of the dicarboxylic acid component (Aa) and the amount of the glycol component (Ab) And when it is 100 mole%, it is 40 mole%. The fluorene copolymerized polyester resin (A-1) is a polyester resin having no dicarboxylic acid component (Aa-3) having a sulfonic acid group.

Reference Example 2 Preparation of Fluorene Copolymerized Polyester Resin (A-1) Water Dispersion (A-1aq)

531.6 parts of water, 2.0 parts of 25% by weight of ammonia water and 33.4 parts of butyl cellosolve were added to 100.0 parts by weight (hereinafter, simply referred to as " part ") of the fluorene copolymerized polyester resin (A- ≪ / RTI > Subsequently, the reaction vessel was sealed, and the inside temperature of the vessel was raised to 120 DEG C and the reaction was carried out for 2 hours to obtain an aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin. The composition of the aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin is shown below.

Fluorene Copolymerized Polyester Resin (A-1): 100 parts (14.993% by weight)

Water: 533.1 parts (79.925% by weight)

Ammonia: 0.5 parts (0.075% by weight)

Butyl cellosolve: 33.4 parts (5.007% by weight).

(Reference Example 3) Adjustment of methylol-type melamine crosslinking agent aqueous dispersion (B-1aq)

(NIKALAC "MW12LF manufactured by SANWA CHEMICAL CO., LTD.) Containing 78.8% by weight of a methylol modified melamine crosslinking agent (B-1) was diluted with water to give the following composition, (B-1aq).

Methylol propane type melamine crosslinking agent (B-1): 25 wt%

Water: 75% by weight.

(Reference Example 4) Adjustment of oxazoline crosslinking agent aqueous dispersion (B-2aq)

(EPOCROS "WS300 manufactured by NIPPON SHOKUBAI CO., LTD.) Containing 10% by weight of an oxazoline crosslinking agent (B-2) was used.

(Reference Example 5) Adjustment of carbodiimide crosslinking agent aqueous dispersion (B-3aq)

An aqueous dispersion (CARBODILITE V04, product of Nisshinbo Holdings Inc.) containing 40 wt% of carbodiimide crosslinking agent (B-3) was diluted with water to give the following composition, and the aqueous dispersion of carbodiimide crosslinking agent (B- 3aq).

Carbodiimide crosslinking agent (B-3): 10 wt%

Water: 90 wt%

(Reference Example 6) Adjustment of colloidal silica aqueous dispersion (C-1aq)

An aqueous dispersion (JGC C & C. "CATALOID" SI80P) containing 40% by weight of colloidal silica was diluted with water to the following composition to obtain a colloidal silica aqueous dispersion (C-1aq).

Colloidal silica: 5 wt%

Water: 95% by weight.

(Reference Example 7) Adjustment of colloidal silica aqueous dispersion (C-2aq)

(SNOWTEX OL manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.) Containing 20% by weight of colloidal silica was diluted with water to the following composition to obtain a colloidal silica aqueous dispersion (C-2aq).

Colloidal silica: 5 wt%

Water: 95% by weight.

(Reference Example 8) Adjustment of surfactant water dispersion (D-1aq)

("Olfine" EXP4051F manufactured by Nissin Chemical Co., Ltd.) containing 50% by weight of an acetylene diol surfactant was diluted with water to the following composition to obtain a surfactant water dispersion (D-1aq).

Surfactant: 5 wt%

Water: 95% by weight.

(Reference Example 9) Preparation of polyester resin (P-1)

(Ab-2) having 60 moles of terephthalic acid, 15 moles of isophthalic acid, 5 moles of sebacic acid and no fluorene skeleton as a dicarboxylic acid component (Aa-2) having no fluorene skeleton under a nitrogen gas atmosphere 40 parts by mol of ethylene glycol, 35 parts by mol of 1,4-butanediol and 25 parts by mol of ethylene glycol were fed into an ester exchange reactor, and tetrabutyl titanate (catalyst) was added to 100 parts by weight of the total dicarboxylic acid component After the esterification reaction was carried out at 160 to 240 ° C for 5 hours, the distillate was removed.

Then, 100 parts by weight of trimellitic acid (20 moles) and tetrabutyl titanate (100 parts by weight) were added as the trivalent or more polyvalent carboxylic acid component (Aa-4) to the total dicarboxylic acid The polyester resin (P-1) was obtained by carrying out a polycondensation reaction under a reduced pressure of 220 to 280 ° C after removing the distillate until it became transparent. The Tg of the polyester resin was 20 占 폚.

The polyester resin (P-1) is a polyester resin in which a component having a fluorene skeleton is not copolymerized. The polyester resin (P-1) is a polyester resin having no dicarboxylic acid component (Aa-3) having a sulfonic acid group.

(Reference Example 10) Preparation of polyester resin (P-1) water dispersion (P-1aq)

Water dispersion was carried out in the same manner as in the fluorene copolymerized polyester resin (A-1) to obtain an aqueous dispersion (P-1aq) of polyester resin.

The composition of the polyester resin aqueous dispersion (P-1aq) is shown below.

Polyester resin (P-1): 100 parts (25.000% by weight)

Water: 299.9 parts by weight (74.975% by weight)

Ammonia: 0.1 part by weight (0.025% by weight).

(Reference Example 11) Preparation of polyester resin (P-2)

(88 mol) of 2,6-naphthalene dicarboxylic acid as the dicarboxylic acid component (Aa-2) having no fluorene skeleton in a nitrogen gas atmosphere and ethylene glycol 90 And 10 parts by mol of diethylene glycol were fed into an ester exchange reactor. 100 parts by weight of tetrabutyl titanate (catalyst) was added to 100,000 parts by weight of the total dicarboxylic acid component, and the mixture was stirred at 160 to 240 DEG C for 5 hours After the esterification reaction, the distillate was removed.

Thereafter, 12 parts by mol of dimethyl 5-sodium sulfoisophthalate as a dicarboxylic acid component (Aa-3) having a sulfonic acid group and 100 parts by weight of tetrabutyl titanate per 100,000 parts by weight of the total dicarboxylic acid component The distillate was removed at 240 ° C. until the reaction product became transparent, and polycondensation reaction was carried out under reduced pressure at 220-280 ° C. to obtain a polyester resin (P-2). The Tg of the polyester resin was 100 deg. The polyester resin (P-2) is a polyester resin in which a component having a fluorene skeleton is not copolymerized. The copolymerization amount of the dicarboxylic acid component (Aa-3) having a sulfonic acid group is 12 mol% based on the amount of the dicarboxylic acid component (Aa).

(Reference Example 12) Preparation of polyester resin (P-2) water dispersion (P-2aq)

200 parts of a polyester resin (P-2) and 150 parts of tetrahydrofuran were dissolved at 80 占 폚, and then 500 parts of water at 80 占 폚 was added to obtain a water / tetrahydrofuran-based solution of the polyester resin (P-2). Further, tetrahydrofuran in the obtained solution was distilled, and after cooling, water was added to obtain an aqueous dispersion (P-2aq) of a polyester resin.

The composition of the polyester resin aqueous dispersion (P-2aq) is shown below.

100 parts (25% by weight) of polyester resin (P-2)

Water: 300 parts (75% by weight).

(Reference Example 13) Preparation of polyester resin (P-3)

The polyester resin (P-3) was obtained in the following copolymer composition by transesterification and polycondensation in the same manner as in the polyester resin (P-2). The Tg of the polyester resin was 100 deg. The polyester resin (P-3) is a polyester resin in which a component having a fluorene skeleton is not copolymerized. The copolymerization amount of the dicarboxylic acid component (Aa-3) having a sulfonic acid group is 1 mol% based on the amount of the dicarboxylic acid component (Aa).

- As the dicarboxylic acid component (Aa-2) having no fluorene skeleton, 2,6-naphthalene dicarboxylic acid

As the glycol component (Ab-2) having no fluorene skeleton, ethylene glycol (90 molar parts), diethylene glycol 10 molar parts

- 1 part by mol of dimethyl 5-sodium sulfoisophthalate as a dicarboxylic acid component (Aa-3) having a sulfonic acid group.

(Reference Example 14) Preparation of polyester resin (P-3) water dispersion (P-3aq)

200 parts of a polyester resin (P-3) and 150 parts of tetrahydrofuran were dissolved at 80 占 폚, and then 500 parts of water at 80 占 폚 was added thereto to obtain a polyester resin (P-3) water / tetrahydrofuran solution. 50 parts of butyl cellosolve was added to the obtained water / tetrahydrofuran system solution, and tetrahydrofuran in the resulting solution was distilled. After cooling, water was added to obtain an aqueous dispersion (P-3aq) of polyester resin.

The composition of the polyester resin aqueous dispersion (P-3aq) is shown below.

Polyester resin (P-3): 100 parts (10% by weight)

Water: 850 parts by weight (85% by weight)

Butyl cellosolve: 50 parts by weight (5% by weight).

(Reference Example 15) Preparation of Fluorene Copolymerized Polyester Resin (A-2)

In the following copolymer composition, transesterification reaction and polycondensation were carried out in the same manner as in the polyester resin (P-2) to obtain a fluorene copolymerized polyester resin (A-2). The Tg of the polyester resin was 130 占 폚. The copolymerization amount of the glycol component (Ab-1) having a fluorene skeleton of the fluorene copolymerizable polyester resin (A-2) is preferably the sum of the amount of the dicarboxylic acid component (Aa) and the amount of the glycol component (Ab) And when it is 100 mole%, it is 40 mole%. The copolymerization amount of the dicarboxylic acid component (Aa-3) having a sulfonic acid group is 5 mol% based on the amount of the dicarboxylic acid component (Aa).

- 90 molar parts of dimethyl 2,6-naphthalenedicarboxylate as the dicarboxylic acid component (Aa-2) having no fluorene skeleton, 5 molar parts of dimethyl isophthalate

- 80 moles of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a glycol component (Ab-1) having a fluorene skeleton

As the glycol component (Ab-2) having no fluorene skeleton, 10 molar parts of ethylene glycol, 10 molar parts of diethylene glycol

5 parts by mol of dimethyl 5-sodium sulfoisophthalate as a dicarboxylic acid component (Aa-3) having a sulfonic acid group.

(Reference Example 16) Preparation of Fluorene Copolymerized Polyester Resin (A-2) Water Dispersion (A-2aq)

20 parts of the above fluorene copolymerized polyester resin (A-2) and 80 parts of tetrahydrofuran were dissolved at 80 占 폚, and then 500 parts of water at 80 占 폚 was added thereto. Thus, the number of polyester resin (A-2) / tetrahydrofuran Solution. (A-2) of polyester resin (A-2) was added to 50 parts of butyl cellosolve to the obtained water / tetrahydrofuran system solution, tetrahydrofuran in the resulting solution was distilled, 2aq).

The composition of the polyester resin aqueous dispersion (A-2aq) is shown below.

Fluorene Copolymerized Polyester Resin (A-2): 100 parts (10% by weight)

Water: 850 parts by weight (85% by weight)

Butyl cellosolve: 50 parts by weight (5% by weight).

(Reference Example 17) Preparation of Fluorene Copolymerized Polyester Resin (A-3)

The polyester resin (A-3) was obtained by transesterification and polycondensation in the following copolymer composition in the same manner as in the polyester resin (A-1). The Tg of the polyester resin was 95 ° C. The copolymerization amount of the glycol component (Ab-1) having a fluorene skeleton of the fluorene copolymerizable polyester resin (A-3) is preferably the sum of the amount of the dicarboxylic acid component (Aa) and the amount of the glycol component (Ab) And when it is 100 mole%, it is 40 mole%. The fluorene copolymerized polyester resin (A-3) is a polyester resin having no dicarboxylic acid component (Aa-3) having a sulfonic acid group.

- Dimethyl succinate (93 mol) as a dicarboxylic acid component (Aa-2) having no fluorene skeleton

- 80 moles of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a glycol component (Ab-1) having a fluorene skeleton

As a glycol component (Ab-2) having no fluorene skeleton, ethylene glycol 20 moles

? 7 parts by mol of 1,2,4,5-benzenetetracarboxylic acid dianhydride as the polyvalent carboxylic acid component (Aa-4) having a valence of 3 or more.

(Reference Example 18) Preparation of Fluorene Copolymerized Polyester Resin (A-3) Water Dispersion (A-3aq)

Aqueous dispersion was carried out in the same manner as in the fluorene copolymerized polyester resin (A-1) to obtain an aqueous dispersion (A-3aq) of fluorene copolymerized polyester resin.

The composition of the aqueous dispersion (A-3aq) of the fluorene copolymerizable polyester resin is shown below.

Fluorene Copolymerized Polyester Resin (A-3): 100 parts (10.000% by weight)

Water: 829.86 parts (82.986% by weight)

Ammonia: 0.14 parts (0.014% by weight)

Butylcellosolve: 70 parts (7.000 wt%).

(Reference Example 19) Preparation of Fluorene Copolymerized Polyester Resin (A-4)

In the following copolymer composition, the transesterification reaction and polycondensation were carried out in the same manner as in the polyester resin (A-1) to obtain a polyester resin (A-4). The Tg of the polyester resin was 94 占 폚. The copolymerization amount of the glycol component (Ab-1) having a fluorene skeleton of the fluorene copolymerizable polyester resin (A-4) is preferably the sum of the amount of the dicarboxylic acid component (Aa) and the amount of the glycol component (Ab) And when it is 100 mole%, it is 40 mole%. The fluorene copolymerized polyester resin (A-4) is a polyester resin having no dicarboxylic acid component (Aa-3) having a sulfonic acid group.

- Dimethyl succinate (93 mol) as a dicarboxylic acid component (Aa-2) having no fluorene skeleton

- 80 moles of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a glycol component (Ab-1) having a fluorene skeleton

As a glycol component (Ab-2) having no fluorene skeleton, ethylene glycol 20 moles

- 7 molar parts of 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride as the polyvalent carboxylic acid component (Aa-4) .

(Reference Example 20) Preparation of aqueous dispersion (A-4aq) of Fluorene Copolymerized Polyester Resin (A-4)

(A-4aq) of a fluorene copolymerized polyester resin was obtained by performing water dispersion in the same manner as in the fluorene copolymerized polyester resin (A-3).

The composition of the aqueous dispersion (A-4aq) of the fluorene copolymerizable polyester resin is shown below.

Fluorene Copolymerized Polyester Resin (A-4): 100 parts (10.000% by weight)

Water: 829.86 parts (82.986% by weight)

Ammonia: 0.14 parts (0.014% by weight)

Butylcellosolve: 70 parts (7.000 wt%).

(Reference Example 21) Preparation of Fluorene Copolymerized Polyester Resin (A-5)

The polyester resin (A-5) was obtained by transesterification and polycondensation in the following copolymer composition in the same manner as in the polyester resin (A-1). The Tg of the polyester resin was 90 占 폚. The copolymerization amount of the glycol component (Ab-1) having a fluorene skeleton of the fluorene copolymerizable polyester resin (A-5) is preferably the sum of the amount of the dicarboxylic acid component (Aa) and the amount of the glycol component (Ab) And when it is 100 mole%, it is 40 mole%. The fluorene copolymerized polyester resin (A-5) is a polyester resin having no dicarboxylic acid component (Aa-3) having a sulfonic acid group.

25 molar parts of dimethyl sebacate and 25 molar parts of dimethyl succinate as the dicarboxylic acid component (Aa-2) having no fluorene skeleton

- 80 moles of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a glycol component (Ab-1) having a fluorene skeleton

As a glycol component (Ab-2) having no fluorene skeleton, ethylene glycol 20 moles

? 50 molar parts of trimellitic acid as the trivalent or more polyvalent carboxylic acid component (Aa-4).

(Reference Example 22) Preparation of fluorene copolymerized polyester resin (A-5) aqueous dispersion (A-5aq)

(A-5aq) of a fluorene copolymerized polyester resin was obtained by performing water dispersion in the same manner as in the fluorene copolymerized polyester resin (A-3).

The composition of the aqueous dispersion (A-5aq) of fluorene copolymerized polyester resin is shown below.

Fluorene Copolymerized Polyester Resin (A-5): 100 parts (14.993% by weight)

Water: 533.1 parts (79.925% by weight)

Ammonia: 0.5 parts (0.075% by weight)

Butyl cellosolve: 33.4 parts (5.007% by weight).

(Reference Example 23) Adjustment of amorphous silica aqueous dispersion (C-3aq)

An aqueous dispersion containing 20% by weight of amorphous silica (NIPPON SHOKUBAI CO., LTD. "KEW30") was diluted with water to the following composition to obtain an amorphous silica aqueous dispersion (C-3aq).

Amorphous silica: 5 wt%

Water: 95% by weight.

Example 1

PET pellets (intrinsic viscosity: 0.63 dl / g) containing substantially no external additive particles constituting the S layer were vacuum dried and then supplied to an extruder and melted at 285 DEG C and extruded from the T- Method, and cooled and solidified by winding on a mirror casting drum having a surface temperature of 25 占 폚. The unstretched film was heated to 90 DEG C and stretched 3.4 times in the longitudinal direction to obtain a uniaxially oriented (uniaxially stretched) film. This film was subjected to a corona discharge treatment in air.

Subsequently, various aqueous dispersions prepared in the above Reference Example were mixed in the following ratios to prepare an aqueous coating agent constituting the C layer. The obtained aqueous coating agent was applied to the corona discharge treated surface of the uniaxially stretched film.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 33.333 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 63.667% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 4.975 wt%

Ammonia: 0.025 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 93.183 wt%

Butylcellosolve: 1.667% by weight.

The uniaxially stretched film coated with an aqueous coating agent was gripped with a clip and introduced into a preheating zone. The film was raised at 110 DEG C using a drying and radiation heater at an ambient temperature of 75 DEG C, dried again at 90 DEG C, The laminate was stretched 3.5 times in the width direction in a heating zone at 120 DEG C and then heat-treated in a heating zone at 220 DEG C for 20 seconds to obtain a laminated polyester film in which the C layer was laminated on the S layer in which crystal orientation was completed. The thickness of the laminated polyester film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of the resultant laminated polyester film are shown in the table. The interference pattern, initial adhesion, and anti-wet heat adhesion index were both good.

Example 2

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 31.667 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 1.000 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 64.333% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 4.726 wt%

Ammonia: 0.024 wt%

Methylrol type melamine crosslinking agent (B-1): 0.250 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 93.267 wt%

Butylcellosolve: 1.583% by weight.

The properties of this laminated film are shown in the table. The coating property was improved by the addition of the crosslinking agent (B), the interference fringe was good, and the initial adhesion and the anti-wet heat adhesion index were very good.

Example 3

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in Table 2. The interference fringe was good, and the initial adhesion and the anti-wet heat adhesion index were very good.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 23.333 wt%

占 methyl roll type melamine crosslinking agent water dispersion (B-1aq): 6.000 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 67.667% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 3.483 wt%

Ammonia: 0.017 wt%

Methylrol type melamine crosslinking agent (B-1): 1.500 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 93.683 wt%

Butylcellosolve: 1.167% by weight.

Example 4

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in the table. The interference fringe was at a practical level, but the initial adhesion and the anti-wet heat adhesion index were very good.

(Water-based coating composition)

Fluorocopolymer polyester resin (A-1aq): 21.667 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 7.000 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 68.333% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 3.234 wt%

Ammonia: 0.016 wt%

Methylrol type melamine crosslinking agent (B-1): 1.750 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 93.767 wt%

Butylcellosolve: 1.083% by weight.

Example 5

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 20 nm. The properties of this laminated film are shown in the table. Both the interference fringe, the initial adhesion and the anti-wet heat adhesion index were very good by optimizing the coating thickness.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 6.333 wt%

≪ tb > Melamine crosslinking agent aqueous dispersion (B-1aq)

Colloidal silica aqueous dispersion (C-2aq): 1.500 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 89.967% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 0.945 wt%

Ammonia: 0.005 wt%

0.050% by weight methylol-type melamine crosslinking agent (B-1)

Colloidal silica: 0.075 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 98.508 wt%

Butylcellosolve: 0.317% by weight.

Example 6

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m and the thickness of the C layer was 2 nm. The properties of this laminated film are shown in the table. The interference pattern, initial adhesion, and anti-wet heat adhesion index were all very good.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 0.6333 wt%

Methylrol type melamine crosslinking agent aqueous dispersion (B-1aq): 0.0200 wt%

Colloidal silica aqueous dispersion (C-2aq): 0.1500 wt%

Surfactant aqueous dispersion (D-1aq): 2.0000 wt%

Water: 97.1967% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 0.0945 wt%

Ammonia: 0.0005 wt%

Methylrol type melamine crosslinking agent (B-1): 0.0050 wt%

Colloidal silica: 0.0075 wt%

Acetylene diol surfactant: 0.1000 wt%

Water: 99.7606 wt%

Butyl cellosolve: 0.0317% by weight.

Example 7

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 1 nm. The properties of this laminated film are shown in the table. The interference fringe was very good, but the initial adhesion and the anti-wet heat adhesion index were at a practical level.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 0.3167 wt%

Methylrol type melamine crosslinking agent aqueous dispersion (B-1aq): 0.0100 wt%

ㆍ Colloidal silica aqueous dispersion (C-2aq): 0.0750 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 97.5983% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 0.0473 wt%

Ammonia: 0.0002 wt%

Methylrol type melamine crosslinking agent (B-1): 0.0025 wt%

Colloidal silica: 0.0038 wt%

Acetylene diol surfactant: 0.1000 wt%

Water: 99.8304 wt%

Butylcellosolve: 0.0158% by weight.

Example 8

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 20 nm. The properties of this laminated film are shown in the table. The interference pattern, initial adhesion, and anti-wet heat adhesion index were all very good.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 6.333 wt%

Aqueous dispersion of oxazoline crosslinking agent (B-2aq): 0.500 wt%

Colloidal silica aqueous dispersion (C-2aq): 1.500 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 89.667% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 0.945 wt%

Ammonia: 0.005 wt%

Oxazoline crosslinking agent (B-2): 0.050 wt%

Colloidal silica: 0.075 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 98.508 wt%

Butylcellosolve: 0.317% by weight.

Example 9

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 20 nm. The properties of this laminated film are shown in the table. The interference pattern, initial adhesion, and anti-wet heat adhesion index were all very good.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 6.333 wt%

Carbodiimide crosslinking agent aqueous dispersion (B-3aq): 0.500 wt%

Colloidal silica aqueous dispersion (C-2aq): 1.500 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 89.667% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 0.945 wt%

Ammonia: 0.005 wt%

Carbodiimide crosslinking agent (B-3): 0.050 wt%

Colloidal silica: 0.075 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 98.508 wt%

Butylcellosolve: 0.317% by weight.

Example 10

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of this laminated film was 100 mu m, and the thickness of the C layer was 200 nm. The properties of this laminated film are shown in the table. The interference fringe was at a practical level, but the initial adhesion and the anti-wet heat adhesion index were very good.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 63.333 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 2.000 wt%

Amorphous silica aqueous dispersion (C-3aq): 2.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 30.667% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 9.452 wt%

Ammonia: 0.048 wt%

Methylrol type melamine crosslinking agent (B-1): 0.500 wt%

Amorphous silica: 0.100 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 86.633 wt%

Butylcellosolve: 3.167% by weight.

Example 11

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 30 nm. The properties of this laminated film are shown in the table. The interference fringe was good, and the initial adhesion and the anti-wet heat adhesion index were very good.

(Water-based coating composition)

Aqueous dispersion (A-1aq) of fluorene copolymerized polyester resin: 9.500 wt%

≪ tb > Melamine crosslinking agent aqueous dispersion (B-1aq): 0.300 wt%

Colloidal silica aqueous dispersion (C-2aq): 2.25 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 85.950% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-1): 1.418 wt%

Ammonia: 0.007 wt%

0.077% by weight methylol-type melamine crosslinking agent (B-1)

Colloidal silica: 0.113 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 97.812 wt%

Butylcellosolve: 0.475% by weight.

Example 12

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 20 nm. The properties of this laminated film are shown in the table. The interference pattern, initial adhesion, and anti-wet heat adhesion index were all very good.

(Water-based coating composition)

Aqueous dispersion of fluorene copolymerized polyester resin (A-3aq): 9.500 wt%

≪ tb > Melamine crosslinking agent aqueous dispersion (B-1aq)

Colloidal silica aqueous dispersion (C-2aq): 1.500 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 86.800% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-3): 0.949 wt%

Ammonia: 0.001 wt%

0.050% by weight methylol-type melamine crosslinking agent (B-1)

Colloidal silica: 0.075 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 98.160 wt%

Butylcellosolve: 0.665% by weight.

Example 13

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 20 nm. The properties of this laminated film are shown in the table. The interference pattern, initial adhesion, and anti-wet heat adhesion index were all very good.

(Water-based coating composition)

Aqueous dispersion of fluorene copolymerized polyester resin (A-4aq): 9.500 wt%

≪ tb > Melamine crosslinking agent aqueous dispersion (B-1aq)

Colloidal silica aqueous dispersion (C-2aq): 1.500 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 86.800% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-4): 0.949 wt%

Ammonia: 0.001 wt%

0.050% by weight methylol-type melamine crosslinking agent (B-1)

Colloidal silica: 0.075 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 98.160 wt%

Butylcellosolve: 0.665% by weight.

Example 14

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in the table. The interference fringe was good, but the initial adhesion and the anti-wet heat adhesion index were at a practical level.

(Water-based coating composition)

Aqueous dispersion (A-5aq) of fluorene copolymerized polyester resin: 33.333 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 63.667% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-5): 4.975 wt%

Ammonia: 0.025 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 93.183 wt%

Butylcellosolve: 1.667% by weight.

Example 15

On the surface of the C layer of the laminated polyester film produced in Example 2, the following paint was applied by a reverse coating method using a small-diameter gravure roll and dried at 90 占 폚.

After drying, an ultraviolet ray (ultraviolet ray) of 400 mJ / cm 2 was applied to a condensing type high pressure mercury lamp (EYE GRAPHICS CO., LTD. Product H03-L31) having an irradiation intensity of 120 W / cm set at a height of 9 cm from the surface of the C layer And hardened to form a high refractive index hard coat layer having a thickness of 2 占 퐉. An industrial UV checker (UVR-N1 manufactured by JAPAN STORAGE BATTERY CO., LTD.) Was used to measure the intensity of UV irradiation. The refractive index of the high refractive index hard-coded layer was 1.67.

(A paint forming a high refractive index hard-coded layer)

ㆍ Pelnox Limited. A coating material Peltron XJC-0357 (2-antimony pentoxide particle / urethane acrylate having an average particle diameter of 30 nm) (refractive index: 1.67) was added to an organic solvent of the following composition so that the solid concentration became 40%

The organic solvent (composition ratio: propylene glycol monomethyl ether / methyl isobutyl ketone / isopropyl alcohol / acetylacetone / toluene = 58 weight% / 19 weight% / 19 weight% / 3 weight% / 1 weight%).

Subsequently, the following low refractive index coating material was applied onto the high refractive index hard coat layer by a reverse coating method using a small-diameter gravure roll and dried at 90 占 폚. After drying, an ultraviolet ray (ultraviolet ray) of 400 mJ / cm < 2 > was applied to a condensing type high pressure mercury lamp (EYE GRAPHICS CO., LTD. Product H03-L31) having an irradiation intensity of 120 W / cm set at a height of 9 cm from the surface of the C layer And cured to provide a low refractive index layer having a thickness of about 100 nm to obtain an antireflection film. The refractive index of the low refractive index layer was 1.37.

(Low refractive index paint)

A paint comprising a JSR product TU2180 (fluorine-based polymer / polyfunctional (meth) acrylate compound / silica fine particles) (refractive index: 1.37) in an organic solvent having the following composition so as to have a solid concentration of 3 wt%.

- Organic solvent (composition ratio: methyl isobutyl ketone / methyl ethyl ketone / isopropyl alcohol / propylene glycol monobutyl ether = 90% by weight / 2% by weight / 2% by weight / 6% by weight).

The interference pattern of the obtained antireflection film was good and the initial adhesion was very good.

Example 16

An antireflection film was produced in the same manner as in Example 15 except that the laminated polyester film produced in Example 5 was used. The interference pattern of the obtained antireflection film was good and the initial adhesion was very good.

Example 17

An antireflection film was produced in the same manner as in Example 15 except that the laminated polyester film produced in Example 11 was used. The interference pattern of the obtained antireflection film was good and the initial adhesion was very good.

Comparative Example 1

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in the table. A component having a fluorene skeleton was not copolymerized with the polyester resin, so that the refractive index of the C layer was not sufficiently high and a strong interference fringe was confirmed.

(Water-based coating composition)

Aqueous dispersion (P-1aq) of polyester resin: 19.000 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 1.000 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.000 wt%

Surfactant aqueous dispersion (D-1aq): 2.000 wt%

Water: 77.000% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (P-1): 4.703 wt%

Ammonia: 0.047 wt%

Methylrol type melamine crosslinking agent (B-1): 0.250 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 94.850% by weight.

Comparative Example 2

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in the table. A component having a fluorene skeleton was not copolymerized with the polyester resin, so that the refractive index of the C layer was not sufficiently high and a strong interference fringe was confirmed. Further, since the polyester resin contains the dicarboxylic acid component (Aa-3) having a sulfonic acid group, the adhesive resistance to moisture and heat is poor.

(Water-based coating composition)

Aqueous dispersion (P-2aq) of polyester resin: 19.00 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 1.00 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.00 wt%

Surfactant aqueous dispersion (D-1aq): 2.00 wt%

Water: 77.000% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (P-2): 4.75 wt%

≪ tb > Melamine cross-linking agent (B-1): 0.25 wt%

Colloidal silica: 0.05 wt%

Acetylene diol surfactant: 0.10 wt%

Water: 94.850% by weight.

Comparative Example 3

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in the table. A component having a fluorene skeleton was not copolymerized with the polyester resin, so that the refractive index of the C layer was not sufficiently high and a strong interference fringe was confirmed. Further, since the polyester resin contains the dicarboxylic acid component (Aa-3) having a sulfonic acid group, the adhesive resistance to moisture and heat is poor.

(Water-based coating composition)

Aqueous dispersion (P-3aq) of polyester resin: 47.50 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 1.00 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.00 wt%

Surfactant aqueous dispersion (D-1aq): 2.00 wt%

Water: 48.50% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (P-3): 4.750 wt%

Methylrol type melamine crosslinking agent (B-1): 0.250 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 92.475 wt%

Butylcellosolve: 2.375% by weight.

Comparative Example 4

A laminated film was obtained in the same manner as in Example 1 except that an aqueous coating agent of the following composition was used. The thickness of the laminated film was 100 mu m, and the thickness of the C layer was 100 nm. The properties of this laminated film are shown in the table. The interference fringe was good, but the polyester resin had a dicarboxylic acid component (Aa-3) having a sulfonic acid group, and thus the adhesive resistance to moisture and heat was poor.

(Water-based coating composition)

Aqueous dispersion (A-2aq) of polyester resin: 47.50 wt%

占 methyl roll type melamine crosslinking agent aqueous dispersion (B-1aq): 1.00 wt%

Colloidal silica aqueous dispersion (C-1aq): 1.00 wt%

Surfactant aqueous dispersion (D-1aq): 2.00 wt%

Water: 48.50% by weight.

The weight ratio of each component in the aqueous coating agent is as follows.

Fluorene Copolymerized Polyester Resin (A-2): 4.750 wt%

Methylrol type melamine crosslinking agent (B-1): 0.250 wt%

Colloidal silica: 0.050 wt%

Acetylene diol surfactant: 0.100 wt%

Water: 92.475 wt%

Butylcellosolve: 2.375% by weight.

≪ Industrial Availability >

The laminated polyester film of the present invention has a layer (S layer) comprising a polyester and a layer (C layer) containing a fluorene copolymerized polyester resin (A), wherein the C- 3 or more and 5 or less, the interference pattern with the hard coat agent made of the active ray-curable resin is suppressed and the adhesion with the hard coat layer under the high temperature and high humidity environment is excellent. Therefore, the hard coat film and the An antireflection film provided with a refractive index layer, a laminated film for a touch panel provided with a conductive metal oxide layer, a laminated film for an electronic paper, and the like.

Claims (8)

(C layer) containing a polyester resin (A) having a fluorene skeleton is directly laminated on a layer (S layer) made of polyester, and the moisture resistance of the surface of the C layer obtained by the following method Wherein the polyester resin (A) has an adhesion index of not less than 3 and not more than 5 and the polyester resin (A) does not have a dicarboxylic acid component (Aa-3) having a sulfonic acid base or a dicarboxylic acid component Is less than 0.1 mol% based on the amount of the polyester resin (Aa), and the polyester resin (A) has a trivalent or more polyvalent carboxylic acid component (Aa-4).
(Method of obtaining anti-wet heat adhesion index)
1. An actinic ray curable resin (Pelnox Limited, product: XJC-0357-1: refractive index 1.67) constituting the hard coat layer was coated uniformly on the laminated polyester film using a bar coater so that the film thickness after curing became 1.5 탆 do.
2. Next, the total irradiation intensity was set to 300 mJ / cm 2 by a condensing type high-pressure mercury lamp (EYE GRAPHICS CO., LTD. Product H03-L31) having an irradiation intensity of 120 W / cm set at a height of 9 cm from the surface of the C layer Ultraviolet rays are irradiated and cured to obtain an optical laminated film in which a hard coat layer is laminated on the laminated film.
3. The resulting laminated optical film for optical is left in a constant-temperature and constant humidity chamber at a temperature of 70 ° C and a relative humidity of 90% for 250 hours to obtain a sample for anti-wet heat adhesion test.
4. Next, 100 cross-cuts of 1 mm 2 are put in the hard coat layer of the sample for anti-wet heat adhesion test. The work is performed in the order of 7 of JIS K5600-5-6 (1999) except for the following points.
ㆍ Test conditions and number of test: Regardless of the requirement in 7.1.1 of JIS K5600-5-6 (1999), test conditions shall be 23 ℃ and relative humidity of 65%. In addition, the number of tests shall be one.
Curing of test plates: Regardless of the requirement in 7.1.2 of JIS K5600-5-6 (1999), curing conditions shall be 23 ℃, relative humidity of 65% and curing time shall be 1 hour.
ㆍ Number of cuts: The number of cuts shall be 11, regardless of the requirement in 7.1.3 of JIS K5600-5-6 (1999).
ㆍ Cut interval: Regardless of the requirement in 7.1.4 of JIS K5600-5-6 (1999), the cut interval is 1mm.
ㆍ Cutting and removal of coating film by manual order: The provisions of 7.2.5 of JIS K5600-5-6 (1999) shall not be applied mutatis mutandis. That is, brushing using a brush is not performed. In addition, in Section 7.2.6 of JIS K5600-5-6 (1999), the provisions of the second paragraph ("the center of the tape is placed in a lattice in a direction parallel to one set of corner cuts as shown in Fig. 3, And the tape shall be flattened with fingers in a length exceeding 20 mm minimum ") and shall not be applied mutatis mutandis to other regulations. Cellotape tape (Cellotape (registered trademark) CT405AP manufactured by NICHIBAN CO., LTD.) Is used as the tape.
ㆍ The tape is attached by using a hand roller (Audio-technica corporation product HP515) and reciprocating three times at a roller moving speed of 5 cm / sec under a load of 19.6 N / m and applying pressure.
5. Then, the tape was peeled off at a rate of 10 cm / sec at a rate of 90 cm with respect to the surface direction of the hard coat layer to perform an adhesion test, and evaluation was carried out in five steps based on the number of remaining grids provided in the hard coat layer, It should be an index.
5: 100/100 (remaining number / number of measurement)
4: 90/100 or more, less than 100/100
3: 80/100 or higher, 90/100 or lower
2: 50/100 or more, less than 80/100
1: less than 50/100. The method according to claim 1,
And the polyvalent carboxylic acid component (Aa-4) is a tetracarboxylic acid. 3. The method according to claim 1 or 2,
Wherein the C layer contains a crosslinking agent (B) and the weight ratio (a) / (b) of the content (a) of the polyester resin (A) and the content of the crosslinking agent (B) / 30 to not more than 95/5. 3. The method according to claim 1 or 2,
The crosslinking agent (B) is at least one crosslinking agent selected from the group consisting of a melamine crosslinking agent, an oxazoline crosslinking agent and a carbodiimide crosslinking agent. 3. The method according to claim 1 or 2,
Wherein the laminated polyester film has a spectral reflectance of 6.0 to 8.3% at a wavelength of 550 nm. 3. The method according to claim 1 or 2,
And the layer thickness of the C layer is 2 to 100 nm. An antireflection film characterized by laminating a layer of a high refractive index hard coat layer and a layer of a low refractive index laminated in this order on the surface of the layer C of the laminated polyester film according to any one of claims 1 to 3 using an active ray curable resin. 8. The method of claim 7,
Wherein the refractive index of the high refractive index hard coat layer is 1.63 to 1.75 and the refractive index of the low refractive index layer is 1.35 to 1.40.